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Solubility and solution enthalpy of a cesium-selective calixarene in supercritical carbon dioxide

Abstract : This paper investigates the solubility of the cesium-selective extractant 25,27-Bis(1-octyloxy)calix[4]arene-crown-6, 1,3-alternate (CalixOctyl) in supercritical CO$_2$ (SC-CO$_2$). A dynamic setup with a solvent loop was used, avoiding any plugging of the solute and allowing precise quantification by UV/visible spectrophotometry. The solubility measurements were carried out between 10.3 and 27.4 MPa at 314, 324 and 334 K. The solubility of CalixOctyl in SC-CO$_2$ ranged from (0.20 $\pm$ 0.02)·10$^{−6}$ mol·mol$^{−1}$ at 334 K and 10.4 MPa to (72.78 $\pm$ 0.31)·10$^{−6}$ mol·mol$^{−1}$ at 324 K and 27.4 MPa, approximately 100 times higher than that of simple $p-t$-butylcalix[4,6,8]arenes and calix[4]arene. The solution enthalpy of CalixOctyl in SC-CO$_2$ was also studied. The heat flow during solubilization at 24.0 MPa and 314, 324 and 334 K was measured by differential scanning calorimetry. The temperature dependence of the solution enthalpy and its extrapolation to any pressure are discussed.
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Adrien Dartiguelongue, Antoine Leybros, Agnès Grandjean. Solubility and solution enthalpy of a cesium-selective calixarene in supercritical carbon dioxide. Journal of Supercritical Fluids, Elsevier, 2017, 125, pp.42-49. ⟨10.1016/j.supflu.2017.01.017⟩. ⟨cea-02380589⟩

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